N-boryl-and n, n&#39;-diboryloxamidines and process of forming same



United States Patent co 3,326,951

Patented June 20, 1967 3,326,957 f N-BORYL- AND N,N-DIBORYLOXAMIDINES N N N N AND PROCESS on FORMING SAME f Swratoslaw Trofimenko, Philadelphia, Pa., assignor to E. I. B X B X du Pont de Nemours and Company, Wilmington, Del., 5 C (If 7 a corporation of Delaware R No Drawing. Filed Apr. 1, 1965, Ser. No. 444,829 I l I 20 Claims. (Cl. 260-462) K. b a, Rb

h. III IV SUE t1s 1nveMnt1on relatesl to am; Class Of h6tercYc1 1c 10 The novel compounds of this invention are named herein ore pa ar It re ates and has as Its from the tetrasubstit-uted oxamidines, i.e., ethanamidines: principal ob ects pIOVlSlOIl of, a new class of monoand diboryloxami-dines and a process for their preparation.

The products of this invention have the formula t Ra R, H a H l l x N N R fi N N1! C l I B X R Rb R V it being understood that formulas analagous to those above Rn Rb can also be used for the oxamidines.

I These products are prepared by reaction of a tetrasubstituted oxamidine (V) with at least an equimolar quanwherein X is hydrogen or BRR'; R R R and R tity of a borane BRR'R" with elimination of HR, prefwhich may be alike or different, are hydrocarbon groups Emmy in the Presence of an inert Solvent of reaction of 1-12 carbon atoms; and R and R, which may be alike medium In the foregoing formulas, a 1 e a, or different, are hydrocarbon groups of 1-12 rb and R have the same significance as in Formula I above; atoms, hydrocarbonoxy groups of 1-12 carbon atoms, represents a hydrocarbon 0f hyd'focafbonoxy group n doro en, or halogen, i.e., fluorine, chlorine, bromine, or g 3 5: g o ps as a n i 10 me. or an yrogen, or ogen, 1.e., uorrne, c 0- The hydrocarbon d hydrocarbonoxy groups of 1.42 rine, bromine, or iodine. The reactivity of groups attached carbon atoms referred to abov r lk l, 1k 1 l to boron when used in this process decreases in the order alkyl, or aryl groups and their oxy, including dioxy, ded hydrogen, alkyl, Y Thus, p on rivatives. Examples of such groups are ethyl, isopropyl, reawon of.fflethylphenylchlofobol'ane y sec.-amyl, n-dodecyl, vinyl, butenyl, cyclohexyl, cyclomethyloxamldlne, the P fl y p x pentyl, p-tolyl, naphthyl, 'p-chlorophenyl, methoxy, ethq l -i g 'F g EE i the oxy, isopropoxy, vinyloxy, n-decanoxy, cyclohexanoxy, is d e orane i fi Oye e and phmoxy 4O orm 0 an a d1t1on product Wit an e er or an amine.

The diboryl tetrasubstituted oxamidines have the for- Equauons for the reactions can be wmten as mula I'td Eli,

N N Rd R, a 1i; Ii 4 H & H+2BRR'R- R\ \C.4 /R t a t" R R, Rb

h! NI! R R t it,

II R R B B 2BR" the R groups being as defined above. p

The above formulas are believed to represent the novel N N products of this invention must satisfactorily, although A other formulas such as charge separation formulas and Rd Re formulas of the type L 1 R R, x H 1 H BRRR" R N, B/ Z X It, Rn b R N \III/ l a IL Rb R N\\\C/N III can be employed. In using a formula like III, it is under- R stood that an exceedingly rapid alternation or equilibrium a lg is implied between two such structures, viz.

It is sometimes desirable, though by no means necessary. to carry out the reaction in a medium or diluent. Suitable media for the reaction are aliphatic and aromatic hydrocarbons, halocarbons, ethers, tertiary amines, and, in general, any liquid devoid of active hydrogen as determined by the Zerewitinoff test. Suitable media, aside from those shown in the examples below, include cyclohexane, n-octane, sym-tetrachloroethane, di-n-butyl ether, and triethylamine.

The process is carried out at a temperature in the range from 20 to 200 C. The preferred temperature for a particular reaction is determined by the nature of the group R" being removed from the borane as HR and is that temperature at which a satisfactory rate of removal is maintained. When R" is halogen, low temperatures, i.e., below room temperature and often below C., are permissible. When R" is a hydrocarbon group, evolution of HR" usually commences in the neighborhood of 100 C., i.e., from about 75l25 C. When R is aryl, higher temperatures up to 200 C. may be required.

While it is possible to run the reaction at super-and subatmospheric pressures, such as pressures in the range of 0.1 atmospheres, pressure is not a critical parameter. The reaction is most conveniently conducted at atmospheric pressure. An inert atmosphere, such as an atmosphere of nitrogen, helium, argon, or methane, is preferred in view of the sensitivity of the boranes to air. It is also advisable to exclude moisture from the reaction.

The following nonlimiting examples illustrate the process and products of the invention in more detail. In these examples the products are characterized by chemical analysis, infrared absorption (IR), and nuclear magnetic resonance (n-m-r). Pressures are ambient atmospheric unless otherwise noted.

EXAMPLE 1 N,N'-bis(dihydr0l20ryl) -synz-letrapr0pyloxamidine (Formula II; R R R R n-C H R, R H) sym-Tetrapropyloxamidine (0.01 mole) and trimethylamineborane (0.02 mole) were heated together until evolution of trimethylamine and hydrogen stopped and the melt refluxed. The melt was poured into a watch glass and cooled to room temperature forming a syrupy liquid. After several days the syrup solidified. The solid was N,N"-bis(dihydroboryl)-sym-tetrapropyloxamidine having a B-H absorption band in the infrared at 2320 cm.

EXAMPLE 2 N,N"-bis(diphenylboryl)-Lsym-tetrapr0pyloxamidinc (Formula II; R,,, R R R =n-C H R, R'- C H A. sym-Tetrapropyloxamidine (0.005 mole) and triphenylborane (0.01 mole) were mixed and heated for minutes at l60-l90 C. The melt bubbled vigorously. The product was purified by sublimation at 300 C. under 2 mm. pressure to obtain N,N"-bis(diphenylboryl)-symtetrapropyloxamidine in 90% yield. After recrystallization and a further sublimation, the product had a melting point of 190 C.

Analysis.-Calcd. for C H B N C, 78.5; H, 8.26; N,

9.62. Found: C, 78.5; H, 8.52; N, 9.37.

The n-m-r spectrum showed a doublet at 2.68 1- (relative area 5), an unresolved triplet at 6.38 -r (relative area 2) and a complex mutiplet at 8.5-9.0 1' (relative area 5) which confirmed the above identification. The ultraviolet absorption in isooctane showed maxima at 270 and 280 my. having extinction coefficients, e, of 28,000 and 25,300 respectively and a shoulder at 293 ma having e:12,100.

B. The above reaction was repeated on a 0.1 molar scale yielding 78% of recrystallized material.

4 EXAMPLE 3 N,N"-bis(diphenylboryl)-sym-tetraelhyloxamidine (Formula II; R R R R =C H R, R'=C H sym-Tetraethyloxamidine (0.005 mole) and triphenylborane (0.01 mole) were heated as in Example 2.. The crude product, obtained in 92% yield, was purified by sublimation.

Analysis.-Calcd. for C H B N C, 77.7; H, 7.62.

Found: C, 78.0; H, 7.65.

The product had a melting point of 250-251 C. The n-m-r spectrum, which showed a doublet (relative area 5) at 2.67 1, a quadruplet (relative area 2) at 6.65 1', and a triplet (relative area 3) at 9.22 T, confirmed that the product was N,N"-bis(diphenylboryl)-sym-tetraethyloxamidine. The ultraviolet absorption spectrum in isooctane showed maxima at 270 and 280 my having extinction coefficients above 27,100 and 24,400 respectively and a shoulder at 293 m with extinction coefiicient above 11,600.

EXAMPLE 4 N ,N "-bis(diethylboryl )-sym-telraethyl0xamidine (Formula II; R,,, R R R R, R==C H A. To a suspension of 9.9 g. (0.05 mole) of symtetraethyloxamidine in ml. benzene, under nitrogen, was added slowly 13.7 ml. (0.1 mole) of triethylborane. Slight warming of the mixture occurred and the solid went quickly into solution. No gas was evolved. The solution was refluxed for three hours, during which time 1.9 liters of gas was evolved. The solution was stripped of low-boiling components and the residue recrystallized from ethanol to yield 6.4 g. of crystalline N,N"-bis-(diethylboryl)-sym-tetraethyloxamidine, M.P. C. The filtrate was purified by chromatography yielding an additional 2.8 g. of product. On heating above the melting point, the melted product remained colorless in air up to 310 C. and became only slightly amber at temperatures above 400 C.

Analysis.-Calcd. for C H B N C, 64.6; H, 12.0; N,

16.7. Found: C, 65.1; H, 11.8; N, 16.4.

The identity of the product was confirmed by its n-m-r spectrum which showed a quadruplet at 6.73 1 (relative area 2), a triplet at 8.72 1- (relative area 3) and an unresolved multiplet centered at 9.53 1' (relative area 5). The ultraviolet spectrum (in isooctane) exhibited a maximum in absorption, A at 279 m having an extinction coeflicient, e, of 18,200.

B. The reaction above was repeated using amounts of reactants and solvent based on 16.6 g. of sym-tetraethyloxamidine with toluene as solvent. The crude product was purified by chromatography on alumina using hexane as the packing and eluting medium. N,N-bis(diethylboryl)-sym-tetraethyloxamidine was obtained in 95.5% yield.

EXAMPLE 5 N ,N -bis (dibromoboryl -.s ym-lelrapr0py loxam'idine (Formula II; R R R R =n-C H R, R=B

To a solution of 10 ml. of boron tribromide, i.e., tribromoborane (26.4 g., 0.105 mole), in 200 ml. of carbon tetrachloride was added a solution of 12.7 g. (0.05 mole) of sym-tetrapropyloxamidine in 300 ml. of toluene. A solid precipitated during the addition. The reaction mixture was left standing for two days at room temperature and then filtered to obtain 26.4 g. (89%) of solid N,N"- bis(dibromoboryl) sym tetrapropyloxamidine. A small sample of the product was purified by recrystallization from chlorobenzene followed by sublimation above 200 C. under 1 mm. pressure.

Analysis.-Calcd. for C H B Br N C, 28.3; H, 4.72;

Br, 53.8. Found: C, 28.9; H, 4.84; Br, 53.5.

The ultravolet absorption spectrum in isooctane had a maximum at 265 111,44. (e 11,500).

EXAMPLE 6 N ,N "-bz's dihydroboryl -sym-tetrameth yloxamid ine (Formula II; R R R R =CH R, R'.=-H)

A mixture of sym-tetramethyloxamidine (0.05 mole) and borane (0.10 mole as a 1.0 molar solution in tetrahydrofuran) and an additional 200 ml. of dry tetrahydrofuran was refluxed overnight. Hydrogen (2.5 liters) was evolved. The solution was concentrated at 65 C. in vacuum yielding a tafly-like residue which was purified by sublimation. The sublimate was obtained was shiny white needles which were recrystallized from n-heptane. The sublimate was N,N"-bis (dihydroboryl)-sym-tetramethyloxamidine, M.P. 169-170 C.

Analysis.Calcd. for C H B N C, 43.4; H, 9.65; N,

33.7. Found: C, 43.6; H, 9.59; N, 33.3.

The ultraviolet absorption spectrum in isooctane had a maximum at 280 m (e=17,400) and shoulders at 288 m (e=15,l) and 302 m (e=6840).

EXAMPLE 7 N,N"-bis(diphenylbo ryl) -sym-tetramethyl0xamidine (Formula II; R,,, R R R =CH R, R'=C H sym-Tetramethyloxamidine (14.2 g., 0.1 mole) and triphenylborane (48.4 g., 0.2 mole) were refluxed together in 250 ml. of o-dichlorobenzene, benzene being fractionally distilled through a small Vigreux column. When benzene ceased to distill out, the hot solution was cooled yielding white crystals which were removed by filtration, washed with ether, and air-dried. These crystals were N,N"-bis(diphenylboryl) sym tetramethyloxamidine, M.P. 280 C. The filtrate was worked up to obtain additional product making a total yield of 86% of theory.

Analysis.Calcd. for C H B N C, 76.6; H, 6.82; N,

11.9. Found: C, 76.5; H, 6.64; N, 11.9

The n-m-r spectrum showed two singlets at 2.77 and 6.99 1' (relative areas 5 and 3, respectively) confirming the identification of the product. The ultraviolet absorption spectrum in isooctane showed maxima at 270 rn,u (e 40,000) and 278 m (E 36,200); and a shoulder at 292 m (e 16,900).

EXAMPLE 8 N,N"-bis(dielhylb0ryl)-sym-tetramethyloxamidine (Formula II; R,,, R R R =CH R, R':C H

Triethylborane (27 ml., 0.19 mole) was added to sym-tetramethyloxamidine (2.14 g., 0.1 mole) in 200 ml. of tetrahydrofuran and the resulting solution was refluxed under nitrogen overnight. The amount of gas evolved was 4.25 liters. The clear solution was evaporated to dryness and the residue recrystallized from toluene yielding 6.5 g. (63%) of N,N"-bis(diethylboryl)-sym-te-trarnethyl oxamidine as colorless crystals, M.P. 160-161" C.

AnaIysis.Calcd. for C H B H C, 60.4; H, 11.5.

Found: C, 59.8; H, 11.4.

A further 7.0 g. (25%) of crude product was obtained by working up the mother liquor. The ultraviolet absorption spectrum in isooctane showed a maximum at 280 m 5:18.100

6 EXAMPLE 9 N,N"-bis(o-phenylenedioxyboryl)-symtetrapropyloxamidine A solution of 11 g. (0.1 mole) of pyroca-techol in ml. of tetrahydrofuran was added slowly to 100 ml. of 21 IN solution of borane in tetrahydrofuran with the evolution of 4.8 liters of hydrogen. A solution of 12.7 g. (0.05 mole) of sym-tetrapropyloxamidine in the least amount of tetrahydrofuran necessary to effect solution was added and the mixture was refluxed overnight. Tetrahydrofuran was then distilled out, replaced by xylene, and refluxing continued for several hours. The crude reaction mixture was chromatographed on alumina using ether for packing and eluting. The first fraction (3.6 g., 16%) was a solid which gave a negative ferric chloride test. Subsequent fractions gave positive tests and were discarded. The product was purified by sublimation at 200 C. under 1 mm. pressure and melted at 245-246 C. It was N,N"- bis o-phenylenedioxyboryl) -sy-m-tetrapropyloxamidine.

Analysis.-Calcd. for C H 'B N O C, 63.7; H, 7.35.

Found: C, 63.8; H, 7.43.

EXAMPLE 10 N-Diphenylbo ryl-sym-tetramethyloxamia'ine (Formula I; R R R R -=CH R, R=C H X=H) A mixture of 14.2 g. (0.1 mole) of'sym-tetramethyloxamidine and 29 g. (0.12 mole) of triphenylborane was refluxed in 250 ml. of dichlorobenzene until benzene ceased to distill out. The solution was stripped of solvent in vacuum and the residue recrystallized from dimethylformamide to obtain 6.4 g. of crystalline solid, which was identified as N,N-bis(diphenylboryl)-symtetramethyloxamidine. The crystallization liquor was chromatographed on alumina and separated into three fractions by successive elution with ether (fraction 1), methylene chloride (fraction 2), and methanol (fraction 3). Fraction 2, which had an infrared absorption at 3250 cm.- characteristic of the NH group, was N-diphenylboryl-sym-tetramethyloxamidine. After recrystallization from toluene, it melted at 230231 C. It was sublimed at 230 C. under a pressure of 1 mm. to obtain a sample for analysis.

Analysis.Calcd. for C -H BN C, 70.6; H, 7.53.

Found: C, 70.5; H, 7.03.

Fraction 1 was an intermediate fraction and fraction 3 was additional N,N-bis (diphenylboryl) -sym-tetramethyloxamidine.

EXAMPLE 11 A solution of 277 g. (1 mole) of N,N'-diphenyloxamidoyl chloride [prepared as described by Bauer, Ber. 40, 3653 (1907)] in 1500 ml. of benzene was added slowly,- and with cooling, to a solution of 425 g. (7 moles) of N- propylamine in 2 liters of benzene. The reaction mixture was left standing overnight, filtered, and the filtrate stripped of low-boiling constituents yielding an oil as residue. This oil was stirred with 500 ml. hexane to precipitate a solid which was filtered, washed with pentane, and air-dried. There was thus obtained 270 g. (91%) of solid N,N"-diphenyl-N,N'-dipropyloxamidine, M.P. 65- 67 C. The identity of this product was confirmed by its n-m-r spectrum which had a complex multiplet centered at 2.80 1- (5 protons), a triplet at 7.10 1- (2 protons), a multiplet at 8.72 'r (2 protons), and a triplet at 9.28 'r (3 protons).

B.N,N"-bis(diphenylboryl) diphenyldipropyloxamidines A mixture of 15 g. (0.05 mole) of N,N"-diphenyl- N',N-dipropyloxamidine (Part A) and 27 g. (0.11 mole) of triphenylborane was refluxed in 150 ml. of o-dichlorobenzene until benzene ceased to distill out. The solvent was evaporated by heating in vacuum. The residue was a mixture of N,N-bis(oiphenylboryl)-N,N-diphenyl-N",N"-dipropyloxamidine and N,N"-bis(diphenylboryl)-N,N"-diphenyl-N,N"'-dipropyloxamidine. This mixture was chromatographed rapidly on alumina, using ether for packing and eluting. The two main fractions so obtained melted at 203-216 C. (A), and about 220 C. (B), respectively.

Analysis.-Calcd. for C H B N Found: Fraction A: C, 81.4; H, 6.92. 81.6; H, 7.14.

The n-m-r spectra support the assigned structures with a 15-proton multiplet centered at 2.8 r, a 2-proton multiplet centered at 7.2 -r, and a 2-proton multiplet centered at 9.5 '1'. (The methyl peak was beyond 10 7'.)

EXAMPLE 12 N,N"-bis(diphenylboryl -sym-tetraphenyloxamidine (Formula II; R R R R R, R' C H A mixture of 39 g. (0.1 mole) of syrn-tetraphenyloxamidine and 53 g. (0.22 mole) of triphenylborane was refluxed in 400 ml. of o-dichlorobenzene until benzene ceased to distill out. The solution was cooled and stirred with 600 ml. of hexane to precipitate a white solid which was filtered and air-dried. The yield was 56.0 g. (78%). Another 7.5 g. of the solid product was obtained by working up the filtrate. The product was purified by sublimation at 280 C. under 1 mm. pressure and melted at 285286 C. remaining undecomposed even at 470 C. It was N,N-bis(diphenylboryl)-sym-tetraphenyloxarnidine.

AnaIysis.-Calcd. for C50H40B2N4: c, 83.5; H, 5.57.

Found: c, 83.7; H, 5.71.

EXAMPLE 13 N,N"-bis(diethy1boryl)-sym-tetraphenyl0xamidine (Formula H; R R R R -C H R, R'=C H A mixture of 78 g. (0.2 mole) of sym-tetraphenyloxamidine and 56 ml. (0.4 mole) of triethylborane in 500 ml. toluene was refluxed for three days under nitrogen. Ten liters of ethane was evolved. The solution so obtained was evaporated to dryness by heating at 100 C. in vacuum, and the residue recrystallized from a mixture of benzene and heptane. A total of 69.6 g. (67.3%) of N,N"- bis(diethylboryl)-sym-tetraphenyloxamidine Was obtained which, after purification by vacuum sublimation, melted at 244-245 C.

Analysis-Calm. for 34H40B2N4i C, H, Found: C, 78.3, H, 7.76.

The n-m-r spectrum of the product with a sharp phenyl singlet at 3.08 -r and a complex ethyl multiplet centered at 9.28 1', both of equal area, confirms this structure.

sym-Tetrasubstituted oxamidines in addition to those of the examples which may be used in the invention, e.g., in the process of Example 3, include: sym-tetra-n-butyloxamidine; sym-tetraisobutyloxamidine; sym-tetraphenyloxamidine; sym-tetra-o-tolyloxamidine; N,-N"-diphenyl-N, N"'-di-o-tolyloxamidine; N,N" diphenyl N',N di-rntolyloxamidine; N,N"-diphenyl N,N"'-di-p-tolyloxamidine; N,N"-di-o-tolyl-N,N"-dim-tolyloxamidine; N,N"- di-o-tolyl-N,N"-di-p-tolyloxamidine; etc.

The table which follows lists additional compounds of the invention (column 3) which may be obtained by reacting boranes (column 1) with sym-tetraethyloxamidine,

C, 81.3; H, 6.78. Fraction B: C,

Still further compounds of the invention are: N,N-bis(dicyclohexylboryl)-sym-tetrapropyloxamidine and N-methylboryl-N"-hydroboryl-N,N"-dicyclohexyl N',N"' dimethyloxamidine.

As is apparent from Formula I, the compounds of this invention fall into two classes, viz., those in which X is hydrogen and those in which X is BRR. Compounds of both classes exhibit opacity or opaqueness towards certain wave lengths of ultraviolet light, i.e., light having a Wave length below 400 millimicrons, and hence are generically useful in protecting light-sensitive or light-fugitive materials against degradation by ultraviolet light. For example, the monoor diboryloxamidines can be incorporated in films and fibers of natural or synthetic organic polymers many of which fail prematurely when exposed intermittently or continuously to ultraviolet light to reduce deterioration of the polymers and/or of dyes used therewith in the presence of ultraviolet light. For this purpose, 0.00110%, preferably 0.015%, of the monoor diboryloxamidine based on the weight of the polymer is normally used. The compounds are also valuable for incorporation in containers, covers for display cases, and the like where protection of the contents from the deleterious action of ultraviolet light is desired. The compounds can be incorporated in polymers by conventional procedures. Certain diboryloxamidines are resistant to thermal degradation and are useful as stable liquids in hydraulic devices exposed to high temperature. The monoboryloxamidines can be polymerized to polymers containing recurring boryloxamidine units.

Since obvious modifications and equivalents in the invention will be evident to those skilled in the chemical arts, I propose to be bound solely by the appended claims.

The embodiment of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A compound of the formula wherein: R,,, R R and R are selected from the group consisting of alkyl, alkenyl, cycloalkyl, aryl, alkoxy, alkenyloxy, cycloalkoxy and aryloxy of up to 12 carbons; and

X is selected from the group consisting of hydrogen and BRR, R and R being selected from the group consisting of hydrogen, halogen, and alkyl, alkenyl, cycloalkyl,

$11 ra N Rn Rs wherein R,,, R R and R are defined as in claim ll, with a borane of the formula BRRR, wherein: R and R are as defined in claim 1; and R is selected from the group consisting of hydrogen, halogen and alkyl, alkenyl, cy-

cloalkyl, aryl, alkoxy, alkenyloxy, cycloalkoxy and aryloxy of 1-12 carbons.

13. The process which comprises reacting, at a temperature in the range 20 to 200 C., syrn-tetrapropyloXamidine with trimethylamineborane.

14. The process which comprises reacting, at a temperature in the range -20 to 200 C., sym-tetrapropyloxamidine with triphenylborane.

15. The process which comprises reacting, at a temerature in the range 20 to 200 C., sym-tetraethyloXamidine with triphenylborane.

16. The process which comprises reacting, at a temperature in the range 20 to 200 C., sym-tetraethyloxamidine with triethylborane.

17. The process which comprises reacting, at a temperature in the range 20 to 200 C., sym-tetrapropyloxaniidine with boron-tribromide.

18. The process which comprises reacting, at a temperature in the range 20 to 200 C., sym-tetramethyloxamidine with borane.

19. The process which comprises reacting, at a temperature in the range -20 to 200 C., sym-tetrapropyloxamidine with borane.

20. The process which comprises reacting, at a temperature in the range 20 to 200 C., N,N"-diphenyl- N,N'-dipropyloxamidine with triphenylborane.

No references cited.

CHARLES B. PARKER, Primary Examiner. BERNARD BILLIAN, Assistant Examiner.

mg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,3 Q,957 Dated June 20, 1967 Inventor) Swiatoslaw Trofimenko It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

[- Col. 3, l. 38, in the name of the compound of Exampl 1, change "N,N'-" to NJ!" and Col. 8, lines 70 and 71 (Claim 1), rewrite "cycloalk aryl. and aryloxy of up" as cycloalkyl and eryl of up SIGNED SEALED (SEAL) Attest:

Edmdmmmh mm B. suaumm, m. Attesting Offioer emission" of Patent! 

1. A COMPOUND OF THE FORMULA
 12. THE PROCESS OF FORMING A COMPOUND OF CLAIM 1 WHICH COMPRISES REACTING, AT A TEMPERATURE IN THE RANGE -20* TO 200*C. A TETASUBSTITUTED OXAMIDINE OF THE FORMULA 